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<p>The current work reports the facile synthesis and characterization of half-sandwich compounds [Ti(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)(Cl)<sub>2</sub>(OR)] (<b>3</b>) (R = <sup><i>i</i></sup>Pr (<b>3a</b>); R = <sup><i>t</i></sup>Bu (<b>3b</b>); R = 2,6-Ph<sub>2</sub>C<sub>6</sub>H<sub>3</sub> (<b>3c</b>); CH<sub>2</sub>CH<sub>2</sub>(<sup><i>C</i></sup>C<sub>4</sub>H<sub>3</sub>S) (<b>3d</b>) (prepared via treatment of Ti(η<sup>5</sup>-C<sub>9</sub>H<sub>7</sub>)Cl<sub>3</sub> (<b>1</b>) with LiOR (<b>2a</b>, R = <sup><i>i</i></sup>C<sub>3</sub>H<sub>7</sub>; <b>2b</b>, R = <sup><i>t</i></sup>C<sub>4</sub>H<sub>9</sub>; <b>2c</b>, R = 2,6-Ph<sub>2</sub>C<sub>6</sub>H<sub>3</sub>; <b>2d</b>, R = CH<sub>2</sub>CH<sub>2</sub>(<sup><i>C</i></sup>C<sub>4</sub>H<sub>3</sub>S)) in a 1:1 molar ratio. Additionally, compounds <b>3a</b>, <b>3b</b>, and <b>3d</b> were also obtained when compound <b>1</b> was reacted with HOR (<b>2a</b>, R = <sup><i>i</i></sup>C<sub>3</sub>H<sub>7</sub>; <b>2b</b>, R = <sup><i>t</i></sup>C<sub>4</sub>H<sub>9</sub>; <b>2d</b>, R = CH<sub>2</sub>CH<sub>2</sub>(<sup><i>C</i></sup>C<sub>4</sub>H<sub>3</sub>S)) under reflux in benzene. The half-sandwich titanium compounds <b>3a</b>–<b>d</b> were characterized by elemental analyses, FT-IR, and <sup>1</sup>H and <sup>13</sup>C{<sup>1</sup>H}-NMR spectroscopy. Density functional theory (DFT) calculations at the B3LYP/6-31G(d) + LANL2DZ level of theory were carried out for <b>1</b> and <b>3a</b>–<b>d</b> in order to better understand and rationalize the nature of bonding and thus demonstrate the effect of different substituents on the structural and electronic properties. The studies confirm a similar complexation pattern despite the different chemical nature of the substituents. However, the HOMO–LUMO frontier molecular orbitals analysis revealed ligand–metal charge transfer, and the calculations predicted smaller HOMO–LUMO energy gaps for <b>3c.</b></p>

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[Ti{η5-C9H7}Cl2(OR)] half-sandwich complexes: synthesis and theoretical studies on substituent effects on the HOMO − LUMO energy gap

  • 期刊论文

  • 发表日期：

    2025年6月18日

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  • Deeb Taher,
  • Sami Klaib,
  • Khaleel I. Assaf,
  • Zakariyya Ishtaiwi,
  • Wissam Helal,
  • Heinrich Lang

摘要

The current work reports the facile synthesis and characterization of half-sandwich compounds [Ti(η5-C9H7)(Cl)2(OR)] (3) (R = iPr (3a); R = tBu (3b); R = 2,6-Ph2C6H3 (3c); CH2CH2(CC4H3S) (3d) (prepared via treatment of Ti(η5-C9H7)Cl3 (1) with LiOR (2a, R = iC3H7; 2b, R = tC4H9; 2c, R = 2,6-Ph2C6H3; 2d, R = CH2CH2(CC4H3S)) in a 1:1 molar ratio. Additionally, compounds 3a, 3b, and 3d were also obtained when compound 1 was reacted with HOR (2a, R = iC3H7; 2b, R = tC4H9; 2d, R = CH2CH2(CC4H3S)) under reflux in benzene. The half-sandwich titanium compounds 3a–d were characterized by elemental analyses, FT-IR, and 1H and 13C{1H}-NMR spectroscopy. Density functional theory (DFT) calculations at the B3LYP/6-31G(d) + LANL2DZ level of theory were carried out for 1 and 3a–d in order to better understand and rationalize the nature of bonding and thus demonstrate the effect of different substituents on the structural and electronic properties. The studies confirm a similar complexation pattern despite the different chemical nature of the substituents. However, the HOMO–LUMO frontier molecular orbitals analysis revealed ligand–metal charge transfer, and the calculations predicted smaller HOMO–LUMO energy gaps for 3c.